EP0806803A1 - Wasserstoffabsorbierende Legierung, Verfahren zu ihrer Herstellung und Elektrode - Google Patents

Wasserstoffabsorbierende Legierung, Verfahren zu ihrer Herstellung und Elektrode Download PDF

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Publication number
EP0806803A1
EP0806803A1 EP97107413A EP97107413A EP0806803A1 EP 0806803 A1 EP0806803 A1 EP 0806803A1 EP 97107413 A EP97107413 A EP 97107413A EP 97107413 A EP97107413 A EP 97107413A EP 0806803 A1 EP0806803 A1 EP 0806803A1
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EP
European Patent Office
Prior art keywords
hydrogen
temperature
rare earth
alloy
ingot
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Granted
Application number
EP97107413A
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English (en)
French (fr)
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EP0806803B1 (de
Inventor
Masahiro c/o Sohgou-kenkyusho Wada
Yoshio c/o Sohgou-kenkyusho Takizawa
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Publication date
Priority claimed from JP8314521A external-priority patent/JPH1025528A/ja
Priority claimed from JP8314522A external-priority patent/JPH10152740A/ja
Application filed by Mitsubishi Materials Corp filed Critical Mitsubishi Materials Corp
Publication of EP0806803A1 publication Critical patent/EP0806803A1/de
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Publication of EP0806803B1 publication Critical patent/EP0806803B1/de
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/383—Hydrogen absorbing alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S420/00—Alloys or metallic compositions
    • Y10S420/90—Hydrogen storage

Definitions

  • the present invention relates to a hydrogen occluding alloy exhibiting significantly high hydrogen absorption and desorption rates, and excellent initial activation characteristics in practical use for electrodes of batteries, for example.
  • the hydrogen occluding alloy is a Ni-based alloy having a reduced composition comprising, by wt% (hereinafter a "%" indicates “wt%”),
  • Hydrogen occluding alloy is typically made by preparing a molten alloy having a given composition and casting it into an ingot.
  • the ingot is subjected to temper annealing in a vacuum or nonoxidizing inert gas atmosphere at a given temperature between 900 and 1,050 °C for a given time period, if necessary, and the as-cast or temper-annealed ingot is mechanically pulverized to a predetermined particle size or pulverized by a hydrogenation process under a pressurized hydrogen atmosphere which includes hydrogen absorption at a given hot temperature between 10 and 200 °C and hydrogen desorption by vacuum evacuation.
  • the battery when the hydrogen occluding alloy is applied to, for example, a battery electrode, the battery can serve a practical use alter a initial activation treatment in a pressurized hydrogen atmosphere for a given time period until the electrode including the hydrogen occluding alloy has a sufficient discharge capacity at a initial stage of use.
  • the hydrogen occluding alloy has been required to have higher hydrogen absorption and desorption rates and a shorter initial activation time than those of the foregoing conventional hydrogen occluding alloy.
  • the present inventors have studied to improve the hydrogen absorption and desorption rates and initial activation of the hydrogen occluding alloy comprising the Ni-based alloy set forth above. As a result, the following conclusion was obtained: When the conventional hydrogen occluding alloy of the as-cast or temper-annealed ingot set forth above is maintained in a hydrogen atmosphere e.g.
  • the alloy at a pressure within the rage from 1 to 2 bar (1 to 2 atms), preferable 1 to 1.2 bar (1 to 1.2 atms) at a temperature within the range of 0°C to 100°C and is subjected to hydrogenation heat treatment in which the alloy is held at a given temperature between 600 and 950 °C, and preferably 700 and 900 °C, for a given time period in a hydrogen atmosphere and cooled, the alloy has a microstructure in which fine rare earth element hydride is dispersively distributed in a CaCu 5 -type crystal matrix.
  • the alloy When the ratio of the rare earth element hydride is 0.5 to 20% by area (for example the upper limit is 10%) by area, the alloy exhibits catalytic effects to remarkably promote hydrogen absorption and desorption without discharge capacity deterioration. Therefore, the alloy can absorb and desorb hydrogen atoms at rats higher than those of the conventional hydrogen occluding alloy, and initial activation is significantly promoted.
  • rare earth elements form a matrix of a CaCu 5 -type crystal structure exhibiting hydrogen occlusion effects together with Ni, and form rare earth element hydride which contributes to increased hydrogen charage and discharge rates and improved initial activation. Since discharge capacity decreases when the content is less than 32% or over 38%, the content is determined to 32 to 38%, preferably 32 to 35% and more preferably 33 to 34%.
  • the Co component is dissolved into a matrix and has effects which reduce volume expansion/shrinkage during hydrogen absorption/desorption, prevent pulverization of the alloy and prolong its usable life.
  • the Co content is less than 0.1%, these desired effect cannot be achieved.
  • the content exceeds 17%, the discharge capacity and initial activation effects tend to decrease. Accordingly, the content is preferably determined to 0.1 to 17%, preferably 4 to 17% and more preferably 6 to 12%.
  • the Al component is dissolved into the matrix and improves the corrosion resistance of the alloy.
  • the content is less than 0.5%, the desired corrosion resistance effects cannot be achieved.
  • the content exceeds 3.5%, the discharge capacity decreases. Therefore, the content is determined to 0.5 to 3.5%, and preferably 1 to 2%.
  • the Mn component is dissolved into the matrix, decreases the equilibrium pressure for dissociating hydrogen, and contributes to increasing discharge capacity.
  • the content is determined to 0.5 to 10%, and preferably 1 to 4.5%.
  • the content is determined to 0.005 to 0.5%, preferably 0.005 to 0.2%, more preferably 0.01 to 0.2% and most preferably 0.01 to 0.08 so that the resulting ratio of rare earth element hydride finely distributed In the matrix is 0.5 to 20% by area, preferably 0.5 to 10% by area, more preferably 0.7 to 9% by area and most preferably 0.7 to 4% by area.
  • the Ni-based hydrogen occluding alloy according to the invention can for example be prepared by melting Ni, La, Ce, Al, Mn and if desired Co, in the desired amounts and/or a corresponding misch metal in a vacuum, casting the melt into a cooled casting mold, maintaining the ingot at a temperature within the range from 0°C to 100°C, in a hydrogen atmosphere, heating and holding the ingot at a temperature within a range from 600°C to 950°C and cooling it to a temperature of 300°C or less.
  • the hydrogen occluding alloy of the present invention can be treated with a temper-annealing alter casting. Temper-annealing at a temperature of e.g.
  • the temper-annealing temperature does not exceed 1050° in order to avoid the possibility that the contents of the alloy change because of vaporization of elements (e.g. Mn) in the alloy. Therefore, the temper-annealing temperature is preferably 850°C to 1050°C.
  • the hydrogen occluding alloy of the present invention is treated in a hydrogen atmosphere alter said casting or alter the possible temper-annealing. Though it is preferable for a said hydrogen treating to the hydrogen occluding alloy to be at room temperature, the same effect can be achieved as much as at 0°C.
  • the alloy does not occlude enough hydrogen so that a reaction of hydrogen and the alloy is not achieved to be even and/or uniform.
  • the hydrogen temperature is determined to 0°C to 100°C, preferable 20°C to 60°C.
  • the hydrogen occluding alloy of the present invention is heated and held after a said hydrogen treating. If the heating and holding temperature is less than 600°C, a reaction for generating rare earth element hydride does not occur. On the other hand, if the heating and holding temperature exceeds 950°C the desired microstructure cannot be achieved because of decomposition of rare earth element hydride. Therefore, the heating and holding temperature is determined to 600°C to 950°C, preferably 700°C to 900°C.
  • Ni, La, Ce, Co, Al and Mn, as well as a misch metal, as raw materials, each preferably having a purity not less than 99.9 % were melted in a vacuum (e.g. in an ordinary high-frequency induction melting furnace) to prepare a Ni-based molten alloy having a given composition and casted into a cooled (e.g. water-cooled) casting mold (e.g. a copper casting mold) to form an ingot.
  • the ingot was temper-annealed at a predetermined temperature within the range from 850°C to 1050°C (e.g. for about for 10 hours). After the ingot was maintained at room temperature (about 20°C) (e.g.
  • alloy(s) of the present invention Hydrogen occluding alloys 1 through 47 in accordance with the present invention (hereinafter referred to as alloy(s) of the present invention) each having a composition set forth in Table 1 through 4 and comprising powder of a particle size of 0.074 mm (200 mesh) or less were prepared in such a way.
  • a conventional hydrogen occluding alloy (hereinafter called "a conventional alloy") having a composition shown in Table 4 was prepared under the same conditions as those for the alloys of the present invention, except that the hydrogenation treatment after temper-annealing was omitted, and alternatively, the alloy was subjected to hydrogenation pulverization involving hydrogen absorption under conditions of a heating temperature of 200°C and a holding time of 1 hour and a hydrogen atmospheric pressure of 8 bar (8 atms) in a pressure vessel and hydrogen desorption by vacuum evacuation, so that the alloy had a particle size of 0.074 mm (200 mesh) or less.
  • a conventional alloy having a composition shown in Table 4 was prepared under the same conditions as those for the alloys of the present invention, except that the hydrogenation treatment after temper-annealing was omitted, and alternatively, the alloy was subjected to hydrogenation pulverization involving hydrogen absorption under conditions of a heating temperature of 200°C and a holding time of 1 hour and a hydrogen atmospheric pressure of 8 bar (8 atm
  • the alloys 1 through 47 of the present invention have a structure in which fine rare earth element hydride is dispersively distributed in a matrix of a CaCu 5 -type crystal structure.
  • the observed ratios (percent by area) of the rare earth element hydride are shown in Tables 1 through 4.
  • X-ray diffraction patterns confirmed that the matrix had a CaCu 5 -type crystal structure and the compound dispersively distributed in the matrix comprises rare earth element hydride.
  • the conventional alloy had a single phase CaCu 5 -type crystal structure.
  • the hydrogen desorption rate was determined by the following procedure: The bath was maintained at a temperature of, for example, 120°C, suitable for hydrogen desorption within a range of from 100 to 300°C, in the state in which measurement of the hydrogen absorption rate had been completed, that is, in the state in which the valves Va and Vb were closed, the valve Vc was opened and the pressure in the system reached a predetermined level of around 20 atms. After, the valve Vb was opened and the valve Vc was closed to evacuate the system, except for the container, to 10 -2 Torr, the valve Vb was closed and the valve Vc was opened. In such a state, the rise in pressure of the system with respect to time was measured.
  • each alloy was used as an active material for a negative electrode of a battery, and the battery was subjected to repeated charge/discharge cycles until the battery showed a maximum discharge capacity as shown below in detail.
  • the initial activation was taken as the number of charge/discharge cycles at which the discharge capacity corresponds to 97% of the maximum discharge capacity.
  • Cuprous oxide (Cu 2 O) as a conductive agent, polytetrafluoroethylene (PTFE) as a binder and carboxymethyl cellulose (CMC) as a thickener were added to each of alloys 1 through 47 of the present invention and the conventional alloy, and the resulting paste was loaded on a commercially available foamed nickel plate having a porosity of 95%.
  • the foamed nickel plate was dried, pressed, and shaped into a cut plate of 30 mm by 40 mm having a thickness of 0.40 to 0.43 mm.
  • the amount of loaded active material was approximately 1.8 g.
  • a nickel thin plate as a lead was welded to a side of the cut plate to form a negative electrode.
  • a positive electrode was formed by preparing a paste from Ni(OH) 2 as an active material, cobalt monoxide (CoO) as a conductive agent, polytetrafluoroethylene (PTFE) as a binder and carboxymethyl cellulose (CMC) as a thickener; loading the paste on the foamed nickel plate; drying, pressing and shaping the foamed nickel plate into a cut plate of 30 mm by 40 mm having a thickness of 0.71 to 0.73 mm; and welding the nickel thin plate to a side of the cut plate.
  • CoO cobalt monoxide
  • PTFE polytetrafluoroethylene
  • CMC carboxymethyl cellulose
  • the positive electrodes were provided on both sides of the negative electrode through separators made of a polypropylene/polyethylene copolymer, and protection plates made of polyvinyl chloride were Integrated therewith at both sides of the positive electrodes so as to prevent omission of the active material from the outside of the positive electrodes.
  • a battery was fabricated by inserting the integrated electrodes into a cell made of polyvinyl chloride and pouring a 28% aqueous KOH solution as an electrolyte solution into the cell.
  • the resulting battery was subjected to charge/discharge cycles under conditions of a charging rate of 0.25 C, discharging rate of 0.25 C, and an amount of charged electric variable corresponding to 135% of the negative electrode capacity.
  • the charge/discharge cycles were repeated until the battery showed a maximum discharge capacity, where one charge and discharge cycle is counted as one charge/discharge.
  • Tables 5 and 6 show the maximum discharge capacity obtained by the procedure set forth above, as well as the number of charge/discharge cycles as a measure evaluating the initial activation, at which the discharge capacity is 97% of the maximum discharge capacity.
  • the hydrogen occluding alloy in accordance with the present invention exhibits significantly high hydrogen absorption and desorption rates, and excellent initial activity in practical use, it significantly contributes to the achievement of high output, high performance, and energy saving in various mechanical apparatuses using the hydrogen occluding alloy.
  • Fig. 1 is a schematic view illustrating the apparatus used for measuring hydrogen absorption ad desorption rates of the hydrogen occluding alloy.
  • [Table 5] Kind Hydrogen absorption rate (wt%/sec.) Hydrogen desorption rate (wt%/sec.) Maximum discharge capacity (mAh/g) Charge/disch arge cycles (Number) Alloys of the present invention 1 0.28 0.25 357 5 2 0.31 0.27 362 3 3 0.33 0.30 355 2 4 0.28 0.26 366 2 5 0.30 0.27 361 3 6 0.29 0.27 358 4 7 0.29 0.26 353 5 8 0.30 0.27 349 5 9 0.31 0.27 366 2 10 0.30 0.26 360 3 11 0.28 0.25 351 4 12 0.29 0.27 354 4 13 0.30 0.27 358 3 14 0.30 0.27 362 2 15 0.29 0.26 361 2 16 0.30 0.26 357 2 17 0.29 0.26 349 3 18 0.29 0.27 359 3 19 0.30 0.27 356 3 20 0.30 0.27

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
EP97107413A 1996-05-09 1997-05-06 Wasserstoffabsorbierende Legierung, Verfahren zu ihrer Herstellung und Elektrode Expired - Lifetime EP0806803B1 (de)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP11476396 1996-05-09
JP11476396 1996-05-09
JP114763/96 1996-05-09
JP8314521A JPH1025528A (ja) 1996-05-09 1996-11-26 水素吸蔵合金
JP314522/96 1996-11-26
JP8314522A JPH10152740A (ja) 1996-11-26 1996-11-26 水素吸蔵合金
JP314521/96 1996-11-26
JP31452196 1996-11-26
JP31452296 1996-11-26

Publications (2)

Publication Number Publication Date
EP0806803A1 true EP0806803A1 (de) 1997-11-12
EP0806803B1 EP0806803B1 (de) 2001-01-31

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EP97107413A Expired - Lifetime EP0806803B1 (de) 1996-05-09 1997-05-06 Wasserstoffabsorbierende Legierung, Verfahren zu ihrer Herstellung und Elektrode

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US (1) US5900334A (de)
EP (1) EP0806803B1 (de)
CN (1) CN1174894A (de)
DE (1) DE69704003T2 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0969110A2 (de) * 1998-06-16 2000-01-05 Mitsubishi Materials Corporation Wasserstoffeinlagerungslegierung
EP1113513A2 (de) * 1999-12-24 2001-07-04 Mitsubishi Materials Corporation Wasserstoffeinlagerungslegierung für eine Batteriekathode

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0867957B1 (de) * 1997-03-28 2008-05-14 Matsushita Electric Industrial Co., Ltd. Negativelektrode für alkalische Akkumulatoren
WO2000001023A1 (fr) * 1998-06-26 2000-01-06 Sanyo Electric Co., Ltd. Alliage absorbeur d'hydrogene pour batteries alcalines et procede de preparation associe
US6120936A (en) * 1998-08-27 2000-09-19 Ovonic Battery Company, Inc. Method for powder formation of a hydrogen storage alloy
TW488106B (en) * 1999-08-05 2002-05-21 Shinetsu Chemical Co Hydrogen absorbing alloy and nickel-metal hydride rechargeable battery
KR100763291B1 (ko) * 2002-04-24 2007-10-04 닛토덴코 가부시키가이샤 시야각 확대 액정표시장치
WO2018123752A1 (ja) * 2016-12-26 2018-07-05 三井金属鉱業株式会社 水素吸蔵合金
CN114107739B (zh) * 2021-11-10 2022-05-10 浙江大学 低滞后高抗粉化能力的固态稀土储氢合金及其制备和应用

Citations (3)

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Publication number Priority date Publication date Assignee Title
EP0550153A2 (de) * 1991-12-25 1993-07-07 Sanyo Electric Co., Limited. Elektrode aus einer wasserstoffabsorbierenden Legierung und Verfahren zu ihrer Herstellung
JPH06212369A (ja) * 1993-01-13 1994-08-02 Sumitomo Metal Ind Ltd Ｎｉ−水素電池用水素吸蔵合金の熱処理方法
EP0622860A2 (de) * 1993-04-28 1994-11-02 SANYO ELECTRIC Co., Ltd. Elektrode aus einer wasserstoffabsorbierenden Legierung

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US4222770A (en) * 1978-03-31 1980-09-16 Agency Of Industrial Science & Technology Alloy for occlusion of hydrogen
US4663143A (en) * 1983-12-21 1987-05-05 Koppers Company, Inc. Hydrogen storage materials of CeNi5-x Mnx alloys
JPH0613401B2 (ja) * 1986-02-10 1994-02-23 松下電器産業株式会社 金属水素化物の製造法
JPH05217578A (ja) * 1992-02-06 1993-08-27 Sanyo Electric Co Ltd 水素吸蔵合金電極の製造方法
JP3212133B2 (ja) * 1992-05-21 2001-09-25 株式会社三徳 希土類金属−ニッケル系水素吸蔵合金鋳塊及びその製造法

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
EP0550153A2 (de) * 1991-12-25 1993-07-07 Sanyo Electric Co., Limited. Elektrode aus einer wasserstoffabsorbierenden Legierung und Verfahren zu ihrer Herstellung
JPH06212369A (ja) * 1993-01-13 1994-08-02 Sumitomo Metal Ind Ltd Ｎｉ−水素電池用水素吸蔵合金の熱処理方法
EP0622860A2 (de) * 1993-04-28 1994-11-02 SANYO ELECTRIC Co., Ltd. Elektrode aus einer wasserstoffabsorbierenden Legierung

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CHEMICAL ABSTRACTS, vol. 121, no. 26, 26 December 1994, Columbus, Ohio, US; abstract no. 304644, KAMINAKA, HIDEYA ET AL: "Heat treatment of hydrogen-absorbing alloys for Ni-hydrogen batteries" XP002035847 *
DATABASE WPI Week 94, Derwent World Patents Index; AN 94-283693 *
DUNBAR J: "HIGH PERFORMANCE NICKEL METAL HYDRIDE BATTERIES", WESCON '94. WESTERN ELECTRONIC SHOW AND CONVENTION, ANAHEIM, SEPT. 27 - 29, 1994, 27 September 1994 (1994-09-27), INSTITUTE OF ELECTRICAL AND ELECTRONICS ENGINEERS, pages 236 - 241, XP000532581 *
LIU F - J ET AL: "SURFACE AND METALLOGRAPHIC MICROSTRUCTURE OF THE LA-ADDED AB2 COMPOUND (TI, ZR)(MNN, CR, NI)2", JOURNAL OF ALLOYS AND COMPOUNDS, vol. 231, no. 1, 15 December 1995 (1995-12-15), pages 392 - 396, XP000548070 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0969110A2 (de) * 1998-06-16 2000-01-05 Mitsubishi Materials Corporation Wasserstoffeinlagerungslegierung
EP0969110A3 (de) * 1998-06-16 2000-01-19 Mitsubishi Materials Corporation Wasserstoffeinlagerungslegierung
EP1113513A2 (de) * 1999-12-24 2001-07-04 Mitsubishi Materials Corporation Wasserstoffeinlagerungslegierung für eine Batteriekathode
EP1113513A3 (de) * 1999-12-24 2001-11-28 Mitsubishi Materials Corporation Wasserstoffeinlagerungslegierung für eine Batteriekathode

Also Published As

Publication number Publication date
CN1174894A (zh) 1998-03-04
EP0806803B1 (de) 2001-01-31
DE69704003D1 (de) 2001-03-08
DE69704003T2 (de) 2001-06-07
US5900334A (en) 1999-05-04

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